Thioether Oxidation with tert-Butyl Hydroperoxide Catalysed by Zr(IV)-Substituted Polyoxometalates | Sciact - CRIS-система Института катализа

Thioether Oxidation with tert-Butyl Hydroperoxide Catalysed by Zr(IV)-Substituted Polyoxometalates Научная публикация

Журнал

Dalton Transactions
ISSN: 1477-9226 , E-ISSN: 1477-9234

Вых. Данные

Год: 2025, Том: 54, Страницы: 2524–12533 Страниц : 10 DOI: 10.1039/d5dt01152c

Ключевые слова

THIANTHRENE 5-OXIDE; OXYGEN-TRANSFER; MECHANISTIC PROBE; ORGANIC SULFIDES; SULFOXIDES; KINETICS; MODEL; H2O2; ACTIVATION; REACTIVITY

Авторы

Zalomaeva Olga V ¹ , Maksimchuk Nataliya V ¹ , Evtushok Vasilii Yu ¹ , Antonov Artem A ¹ , Yanshole Vadim V ² , Kholdeeva Oxana A ¹

Организации

1	Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russia
2	International Tomography Centre SB RAS, Novosibirsk 630090, Russia

Информация о финансировании (1)

Российский научный фонд

23-13-00156

Zr-substituted polyoxometalates (Zr-POMs) with Lindqvist, Keggin and Wells–Dawson structures, (Bu4N)6[{W5O18Zr(μ-OH)}2] (Zr-L), (Bu4N)8[{PW11O39Zr(μ-OH)}2] (Zr-K) and (Bu4N)11H3[{P2W17O61Zr(μ-OH)}2] (Zr-WD), can activate the environmentally friendly oxidant tert-butyl hydroperoxide (TBHP) and efficiently catalyse the oxidation of various thioethers to produce sulfoxides and sulfones. Ti- and Nb-substituted POMs are significantly less active than Zr-POMs. The activity and selectivity of Zr-POMs strongly depend on their structural type. The reaction rate decreases when moving from Zr-K and Zr-WD to Zr-L. With 1 equiv. of TBHP, the main product of Zr-K is sulfoxide, whereas sulfone predominates with Zr-L. The reaction mechanism was probed using test substrates, and kinetic, isotopic (H218O), and spectroscopic methods. Monomeric alkylperoxo complexes bearing one tert-butyl peroxo moiety per Zr-POM were obtained by the reaction of Zr-K and Zr-L with TBHP and characterized by elemental analysis, HR-ESI-MS, ATR-FT-IR and multinuclear NMR spectroscopy. Both Zr-K and Zr-L alkylperoxo complexes revealed activity toward thioethers under stoichiometric conditions and produced predominantly sulfoxides, pointing to an electrophilic oxygen transfer mechanism. Under turnover conditions, binding of sulfoxide to Zr-L masks the electrophilic character of oxidation and increases the yield of sulfone. The solvent nature strongly affects the oxygen transfer mechanism and oxidation selectivity.

Zalomaeva O.V. , Maksimchuk N.V. , Evtushok V.Y. , Antonov A.A. , Yanshole V.V. , Kholdeeva O.A.
Thioether Oxidation with tert-Butyl Hydroperoxide Catalysed by Zr(IV)-Substituted Polyoxometalates
Dalton Transactions. 2025. V.54. P.2524–12533. DOI: 10.1039/d5dt01152c WOS Scopus OpenAlex

Поступила в редакцию:	16 мая 2025 г.
Принята к публикации:	16 июл. 2025 г.
Опубликована online:	19 июл. 2025 г.
Опубликована в печати:	19 авг. 2025 г.

Web of science:	WOS:001537357200001
Scopus:	2-s2.0-105013671229
OpenAlex:	W4412726542

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